Origin of the vibrational structure of the first absorption band of cis/trans isomeric 1,6-diphenylhexatrienes by (TD)DFT calculations

We present a detailed spectroscopic analysis of the first absorption band of the six possible conformers of 1,6-diphenyl-1,3,5-hexatriene, obtained by changing the configuration of trans double bonds to cis. To this end, we computed the absorption spectra using FCclasses 3.0 code. First, we assessed...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2024-09, Vol.161 (12)
Main Authors: Martin-Somer, Ana, Catalán, Javier
Format: Article
Language:English
Subjects:
Absorption spectra
Density functional theory
Shape effects
Temperature effects
Citations: Items that this one cites
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:We present a detailed spectroscopic analysis of the first absorption band of the six possible conformers of 1,6-diphenyl-1,3,5-hexatriene, obtained by changing the configuration of trans double bonds to cis. To this end, we computed the absorption spectra using FCclasses 3.0 code. First, we assessed the performance of PBE0 and CAM-B3LYP density functional theory functionals with different basis sets to reproduce the experimental spectra. Additionally, we considered different models to compute the spectra. PBE0/def2tZVP with an adiabatic hessian model with internal coordinates yields results in very good agreement with experimental data. Subsequently, we analyzed the different contributions of vibronic transition to the spectral structure, correlating ground state conformation with spectral shape, and studied the effect of temperature on the absorption first band.
ISSN:0021-9606
1089-7690
1089-7690
DOI:10.1063/5.0221196